ナノポーラス金属触媒を用いた反応集積化法の開発

• Project Area: Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
• Project/Area Number: 22106502
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tohoku University
• Principal Investigator: 浅尾 直樹 東北大学, 原子分子材料科学高等研究機構, 教授 (60241519)
• Project Period (FY): 2010 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2011: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2010: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: ナノポーラス金 / フロー合成 / アルコール酸化反応 / マイクロリアクター / 触媒カラム / 触媒反応 / 不均一系触媒 / 有機シラン化合物 / 有機シラノール化合物

Research Abstract

報告者は、前年度にナノポーラス金の作成法を検討し、有機シラン化合物の酸化反応においてこの金属材料が優れた触媒として機能することを明らかにした。そこで今年度は、本申請研究の目的であるフロー合成に本金属材料触媒を適用するべく検討を行った。まずフロー合成に適する反応としてアルコールの酸素酸化反応に注目し、この反応における本金属材料の触媒活性を調べた。その結果、酸素風船による酸素雰囲気下メタノール溶媒を用いると、様々な2級アルコールが温和な条件下で酸化され、対応するケトン体が高収率で得られることを見出した。他の金の固体触媒としては、金微粒子による酸素酸化反応が既に広く研究されているが、一般に過剰量の塩基を添加する必要がある。これに対し本触媒反応は、そのような添加剤を何も加えなくても反応が進行するため、操作が極めて容易である。またこのことから、ナノポーラス金によるアルコール酸化は、金微粒子触媒の場合と異なる反応機構を経由していることがわかる。続いて本反応をフロー合成に適用した。まず内径2mm、長さ15cmのステンレス鋼製のチューブに粉末状のナノポーラス金を詰めて触媒カラムを作成した。二本のシリンジにそれぞれアルコール溶液と酸素ガスを詰めて、マイクロリアクターで混合した後、触媒カラムを通過するようにフローシステムを作成した。その結果、シリンジポンプを用いてアルコールと酸素を押し出し、触媒カラムから出てきた生成物を解析したところ、収率よく生成物が得られることを見出し、しかもフラスコを用いたバッチシステムよりも、反応時間を大幅に短縮することができた。
以上の結果は、ナノポーラス金触媒を用いたアルコールの酸素酸化が、気相-液相-固相の三相系によるフロー合成に適していることを示しており、本申請研究の目的を達成することができた。

Research Products

• [Journal Article] Aerobic oxidation of alcohols in the liquid phase with nanoporous gold catalysts (2012)
  • Author(s): Asao, N.; Hatakeyama, N.; Menggenbateer, Minato, T.; Ito, E.; Hara, M.; Kim, Y.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Chem.Commun. Volume: 48 Issue: 38 Pages: 4540-4542
  • DOI: 10.1039/c2cc17245c
  • Peer Reviewed
• [Journal Article] Donor-acceptor Dyes Incorporating Stable Dibenzosilole π-Conjugated Spacer for Dye-sensitized Solar Cells (2012)
  • Author(s): Akhtaruzzaman, Md.; Seya, Y.; Asao, N.; Islam, A.; Kwon, E.; El-Shafei, A.; Han, L.; Yamamoto, Y.
  • Journal Title: J.Mater.Chem. Volume: (印刷中) Issue: 21 Pages: 10771-10778
  • DOI: 10.1039/c2jm30978e
  • Peer Reviewed
• [Journal Article] Nanoporous Gold-Catalyzed [4+2] Benzannulation between ortho-Alkynylbenzaldehydes and Alkynes (2012)
  • Author(s): Asao, N.; Menggenbateer, Seya, Y.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Synlett Volume: 23 Issue: 01 Pages: 66-69
  • DOI: 10.1055/s-0031-1289527
  • Peer Reviewed
• [Journal Article] A novel metal-free panchromatic TiO_2 sensitizer based on a phenylenevinylene-conjugated unit and an indoline derivative for highly efficient dye-sensitized solar cells (2011)
  • Author(s): Akhtaruzzaman, Md.; Islam, A.; Yang, F.; Asao, N.; Kwon, E.; Singh, S.P.; Han, L.; Yamamoto, Y.
  • Journal Title: Chem.Commun. Volume: 47 Issue: 45 Pages: 12400-12402
  • DOI: 10.1039/c1cc15580f
  • Peer Reviewed
• [Journal Article] Reusable and Sustainable Nanostructured Skeleton Catalyst : Heck Reaction with Nanoporous Metallic Pd (PdNPore) as a Support, Stabilizer and Ligand Free Catalyst (2011)
  • Author(s): Kaneko, T.; Tanaka, S.; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Adv.Synth.Catal. Volume: 353 Pages: 2927-2932
  • Peer Reviewed
• [Journal Article] Formation and properties of Au-based nanograined metallic glasses (2011)
  • Author(s): Chen, N.; Frank, R.; Asao, N.; Louzguine-Luzgin, D.V.; Sharma, P.; Wang, J.Q.; Xie, G.Q.; Ishikawa, Y.; Hatakeyama, N.; Lin, Y.C.; Esashi, M.; Yamamoto, Y.; Inoue, A.
  • Journal Title: Acta Mater. Volume: 59 Issue: 16 Pages: 6433-6440
  • DOI: 10.1016/j.actamat.2011.07.007
  • Peer Reviewed
• [Journal Article] Gold-catalyzed alkylation of silyl enol ethers with ortho-alkynylbenzoic acid esters (2011)
  • Author(s): Aikawa, H.; Kaneko, T.; Asao, N.; Yamamoto, Y.
  • Journal Title: Beilstein J.Org.Chem. Volume: 7 Pages: 648-652
  • DOI: 10.3762/bjoc.7.76
  • Peer Reviewed
• [Journal Article] A nanostructured skeleton catalyst : Suzuki-coupling with a reusable and sustainable nanoporous metallic glass Pd-catalyst (2011)
  • Author(s): Tanaka, S.; Kaneko, T.; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Chem.Commun. Volume: 47 Issue: 21 Pages: 5985-5987
  • DOI: 10.1039/c1cc10710k
  • Peer Reviewed
• [Journal Article] Stat3 as a Therapeutic Target for the Treatment of Psoriasis : A Clinical Feasibility Study with STA-21, a Stat3 Inhibitor (2011)
  • Author(s): Miyoshi, K.; Takaishi, M.; Nakajima, K.; Ikeda, M.; Kanda, T.; Tarutani, M.; Iiyama, T.; Asao, N.; DiGiovanni, J.; Sano, S.
  • Journal Title: J.Invest.Dermatology Volume: 131 Pages: 108-117
  • Peer Reviewed
• [Journal Article] Nanostructured Materials as Catalysts : Nanoporous-Gold-Catalyzed Oxidation of Organosilanes with Water (2010)
  • Author(s): Asao, N.; Ishikawa, Y.; Hatakeyama, N.; Menggenbateer, Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Journal Title: Angew.Chem.Int.Ed. Volume: 49 Pages: 10093-10095
  • Peer Reviewed
• [Presentation] Nanoporous materials as skeleton catalysts for molecular tran sformations (2012)
  • Author(s): Asao, N.
  • Organizer: UCSB ICMR/CNSI and Tohoku University Joint Workshop
  • Place of Presentation: Santa Barbara, USA(招待講演)
• [Presentation] Mechanism of organic chemical reactions on nano-porous gold (2012)
  • Author(s): Minato, T.; Ito, E.; Ishikawa, Y.; Hatakeyama, N.; Hara, M.; Kim, Y.; Asao, N.; Yamamoto, Y.
  • Organizer: Towards Reality in Nanoscale Materials V
  • Place of Presentation: Levi, Finland
• [Presentation] ナノポーラスPdを触媒とするHeck反応の開発 (2011)
  • Author(s): 金子哲朗・浅尾直樹・山本嘉則・陳明偉・張偉・井上明久
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(神奈川県)
  • Year and Date: 2011-03-28
• [Presentation] ナノポーラス金触媒を用いたアルコールの酸素酸化反応 (2011)
  • Author(s): 畠山直也・孟根巴特尓・浅尾直樹・山本嘉則・陳明偉・張偉・井上明久
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(神奈川県)
  • Year and Date: 2011-03-28
• [Presentation] ナノポーラスPdを触媒とする鈴木カップリング反応の開発 (2011)
  • Author(s): 田中信也・浅尾直樹・山本嘉則・陳明偉・張偉・井上明久
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(神奈川県)
  • Year and Date: 2011-03-28
• [Presentation] ナノポーラス金触媒を用いた有機シラン化合物の酸化反応 (2011)
  • Author(s): 石川敬章・畠山直也・孟根巴特尓・浅尾直樹・山本嘉則・陳明偉・張偉・井上明久
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(神奈川県)
  • Year and Date: 2011-03-27
• [Presentation] 二酸化チタンの表面欠陥の原子レベルでの物性解明 (2011)
  • Author(s): 湊丈俊・Pang Chi Lun・梶田晴司・浅尾直樹・山本嘉則・中山隆・川合真紀・金有洙
  • Organizer: 日本物理学会第66回年次大会
  • Place of Presentation: 新潟大学(新潟県)
  • Year and Date: 2011-03-25
• [Presentation] Nanoporous Metallic Materials as Effective Green Catalysts for Molecular Transformations (2011)
  • Author(s): Asao, N.
  • Organizer: The 2011 WPI-AIMR Annual Workshop
  • Place of Presentation: 仙台国際センター(宮城県)
  • Year and Date: 2011-02-22
• [Presentation] Aerobic Oxidation of Alcohols Catalyzed by Nanoporous Gold (2011)
  • Author(s): Hatakeyama, N.; Menggenbateer; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Organizer: 16th IUPAC International Symposium on Organ ometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
• [Presentation] Nanoporous gold as a catalyst for the oxidation of organosilanes (2011)
  • Author(s): Ishikawa, Y.; Hatakeyama, N.; Menggenbateer; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Organizer: 16th IUPAC International Symposium on Organ ometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
• [Presentation] Nanostructured Skeleton Catalyst : Suzuki-coupling and Heck Reaction with Nanoporous Pd-catalyst as a Non-supported Catalyst (2011)
  • Author(s): Tanaka, S.; Kaneko, T.; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.: Inoue, A.
  • Organizer: 16th IUPAC International Symposium on Organ ometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
• [Presentation] Nanoporous Gold Catalyzed Benzannulation Reaction (2011)
  • Author(s): Menggenbateer; Asao, N.; Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Organizer: 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
• [Presentation] Nanoporous Metallic Materials as Effective Green Catalysts for Molecular Transformations (2011)
  • Author(s): Asao, N.
  • Organizer: 14th Asian Chemical Congress 2011 (14 ACC)
  • Place of Presentation: Bangkok, Thailand(招待講演)
• [Presentation] Integrated Aerobic Oxidation of Alcohols Catalyzed by Nanoporous Gold (2011)
  • Author(s): Asao, N.; Hatakeyama, N.; Yamamoto, Y.
  • Organizer: The Seventh International Symposium on Integrated Synthesis (ISIS-7)
  • Place of Presentation: Kobe, Japan
• [Presentation] Nanoporous Metals as Effective Catalysts for Molecular Transformations (2011)
  • Author(s): Asao, N.
  • Organizer: Tateshina Conference on Organic Chemistry 2011
  • Place of Presentation: Tateshina, Japan
• [Presentation] Molecular transformation with nanoporous materials skeleton catalysts (2011)
  • Author(s): Asao, N.
  • Organizer: Frontier Materials and Processes (Frontier 2011)
  • Place of Presentation: Sendai, Japan(招待講演)
• [Presentation] Atomic defect control on titanium dioxide surface by scanning tunneling microscopy (2011)
  • Author(s): Minato, T.; Pang, C.-L.; Kajita, S.; Asao, N.; Yamamoto, Y.; Nakayama, T.; Kawai, M.; Kim, Y.
  • Organizer: International Symposium on Surface Science (ISSS-6)
  • Place of Presentation: Tokyo, Japan
• [Presentation] Gold-catalyzed functionalization of silyl enol ethers (2010)
  • Author(s): Kaneko, T.; Aikawa, H.; Asao, N.
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2010-12-18
• [Presentation] Oxidation of alcohols with molecular oxygen catalyzed by reusable nanoporous gold (2010)
  • Author(s): Asao, N.; Ishikawa, Y.; Hatakeyama, N.; Menggenbateer, Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2010-12-18
• [Presentation] Gold-catalyzed dehydration of alcohols (2010)
  • Author(s): Seya, Y; Umetsu, K.; Asao, N.
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2010-12-16
• [Presentation] Individual Hydrogen Desorption from Titanium Dioxide Surfaces (2010)
  • Author(s): Minato, T.; Pang, C.-L.; Asao, N.; Yamamoto, Y.; Kawai, M.; Kim, Y.
  • Organizer: Asian Conference on Nanoscience & Nanotechnology (AsiaNANO 2010)
  • Place of Presentation: 日本科学未来館(東京都)
  • Year and Date: 2010-11-02
• [Presentation] Gold-catalyzed dehydration of alcohols (2010)
  • Author(s): Seya, Y.; Umetsu, K.; Asao, N.
  • Organizer: 24th International Conference on Organometallic Chemistry (ICOMC 2010)
  • Place of Presentation: Taipei, Taiwan
  • Year and Date: 2010-07-19
• [Presentation] Nanoporous Gold as an Effective Heterogeneous Catalyst for Molecular Transformations (2010)
  • Author(s): Asao, N.; Ishikawa, Y.; Hatakeyama, N.; Menggenbateer, Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A.
  • Organizer: WCU/AMS (POSTECH)-WPI/AIMR (TOHOKU Univ) Joint Workshop
  • Place of Presentation: Pohang, Korea
  • Year and Date: 2010-06-18